CN111054301B - Remediation method of heavy metal polluted surface water - Google Patents
Remediation method of heavy metal polluted surface water Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a method for restoring surface water polluted by heavy metal, which comprises the following steps: adsorbing heavy metal polluted surface water by using a magnetic adsorbent, carrying out magnetic separation on the magnetic adsorbent adsorbing the heavy metal and the purified surface water, adsorbing the magnetic adsorbent on a magnetic plate, and feeding the purified surface water into a clean water tank; the magnetic adsorbent on the magnetic plate is physically regenerated and reused. The surface water treated by the method reaches the environmental quality standard of the surface water, the adsorbent can be recycled, and the treatment cost is low; the adsorption efficiency is high, and the treated water amount is large; bottom mud containing heavy metal pollution is not generated, and secondary pollution is avoided.
Description
Technical Field
The invention belongs to the technical field of sewage and wastewater treatment, and particularly relates to a surface water heavy metal pollution remediation technology which is used for treatment and remediation of heavy metal polluted surface water bodies and emergency treatment of surface water heavy metal pollution events, and is particularly suitable for remediation and treatment of heavy metal polluted surface water such as mercury, cadmium, lead, arsenic, thallium, copper, zinc, nickel, antimony and the like.
Background
At present, in the aspects of treatment and restoration of heavy metal polluted surface water bodies, the adopted modes mainly comprise medicament addition and phytoremediation. In the aspect of emergency treatment of surface water heavy metal pollution events, the adopted mode is mainly medicament addition. The adoption of a medicament adding mode has the following problems: (1) a large amount of heavy metals and medicaments are subjected to chemical reaction, and are precipitated to the bottom of a river to form bottom mud, so that serious secondary pollution is easily caused; (2) the chemical agent is excessively added in a large amount, and the cost is high. The following problems exist with phytoremediation: (1) the repairing process is long, the effect is slow, and the treatment of the plants after heavy metal adsorption is easy to cause serious secondary pollution; (2) plant maintenance is complex and requires a large amount of manpower. Therefore, the adoption of the surface water heavy metal pollution remediation technology cannot meet the increasingly strict environmental protection requirement, and a new surface water heavy metal pollution remediation technology is urgently needed to be developed to ensure the water quality safety of the surface water body.
Chinese patent application CN103623782A discloses a method for preparing a composite magnetic adsorption material and removing heavy metal ions in wastewater. The preparation method comprises the following steps: (1) Finely grinding the magnetic seeds in a pulverizer to submicron magnetic particles; (2) Mixing magnetic particles, a high-molecular natural material with heavy metal adsorption performance and a solvent, adding a coagulant, uniformly mixing, and reacting to obtain a spherical composite magnetic product; (3) And carrying out magnetic separation, washing and drying on the composite magnetic product to obtain the composite magnetic adsorption material. Adding the magnetic adsorption material into the wastewater containing the heavy metal ions, stirring, adsorbing, reacting, performing magnetic separation by using a magnetic separator to adsorb the magnetic material containing the heavy metal ions, and recovering the heavy metals. However, the magnetic adsorption material prepared by the method mainly depends on the selective adsorption of specific heavy metals by organic groups, and desorption and recovery.
Disclosure of Invention
The invention aims to provide a method for restoring surface water polluted by heavy metal, which develops the research of surface water heavy metal pollution restoration technology aiming at the water quality characteristics of surface water body polluted by heavy metal, and provides a surface water heavy metal pollution restoration technology of 'magnetic adsorbent adsorption', wherein the surface water after treatment reaches the surface water environment quality standard, the adsorbent can be recycled, and the treatment cost is low; the adsorption efficiency is high, and the treated water amount is large; bottom mud containing heavy metal pollution is not generated, and secondary pollution is avoided.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a remediation method of heavy metal contaminated surface water, the remediation method comprising the steps of:
adsorbing heavy metal polluted surface water by using a magnetic adsorbent, carrying out magnetic separation on the magnetic adsorbent adsorbing the heavy metal and the purified surface water, adsorbing the magnetic adsorbent on a magnetic plate, and feeding the purified surface water into a clean water tank; the magnetic adsorbent on the magnetic plate is regenerated and reused.
Preferably, during the adsorption treatment of the magnetic adsorbent, the dosage of the magnetic adsorbent is 200 mg/L-400 mg/L, and the adsorption time is 30min-60min.
In the process of treating heavy metal polluted surface water by magnetic adsorption, 1-3 wt% of magnetic adsorbent used for the first treatment can be discharged together with sludge, and simultaneously 1-3 wt% of new magnetic adsorbent is supplemented and mixed with the magnetic adsorbent used and regenerated before to be used as the adsorbent for the second treatment, and the operation is repeated; and the magnetic adsorbent after regeneration treatment can be subjected to secondary adsorption treatment.
Preferably, the external magnetic field for magnetic separation is 0.1-0.5T.
Preferably, the regeneration is in particular: the magnetic adsorbent is in a fluidized state, sludge on the magnetic adsorbent is removed, and the regeneration time is 30-60 min. The invention can adopt the method that the magnetic adsorbent is placed in a magnetic adsorbent regenerator to be in a fluidized state, then the peripheral friction brush cloth is used for rotating and flexibly rubbing to remove the sludge, and the friction brush cloth is a commercial product and can be obtained by market purchase.
Preferably, the preparation method of the magnetic adsorbent comprises the following steps:
1) Putting 30-100 mesh porous ceramic particles into 0.3-0.6 mol/L manganese salt aqueous solution which is 3-5 times of the volume of the porous ceramic particles to soak for 1-2 hours to prepare manganese-loaded porous ceramic particles;
2) Putting the manganese-loaded porous ceramic particles into 0.1-0.2 mol/L cerous nitrate solution which is 3-5 times of the volume of the manganese-loaded porous ceramic particles, and soaking for 1-2 hours to prepare the manganese-loaded cerium porous ceramic particles;
3) Putting the manganese-cerium-loaded porous ceramic particles into 0.5-1 mol/L potassium permanganate solution which is 3-5 times of the volume of the manganese-cerium-loaded porous ceramic particles, soaking for 1-2 hours, and cleaning for 10-30 minutes to prepare manganese-cerium-oxide-loaded porous ceramic particles;
4) Putting the porous ceramic particles carrying manganese oxide cerium into 0.8-1.2 mol/L ferric salt aqueous solution which is 3-5 times of the volume of the porous ceramic particles carrying manganese oxide cerium, and soaking for 1-2 hours to prepare the porous ceramic particles carrying iron, manganese and cerium;
5) Putting the Fe-Mn-Ce-carried porous ceramic particles into 1-2 mol/L sodium hydroxide solution with the volume 3-5 times of that of the Fe-Mn-Ce-carried porous ceramic particles for aeration oxidation reaction for 2-3 hours at the reaction temperature of 40-80 ℃ to prepare magnetic Fe-Ce-Mn-carried porous ceramic particles;
6) And (3) washing the magnetic iron-cerium-manganese-loaded porous ceramic particles with clear water for 10-30 minutes, and air-drying at normal temperature for 1-3 days to obtain the magnetic adsorbent.
Further preferably, the manganese salt is manganese sulfate and/or manganese chloride.
Further preferably, the iron salt is a ferrous salt and a ferric salt, and the ferrous salt is ferrous sulfate and/or ferrous chloride; the ferric salt is ferric sulfate and/or ferric chloride.
The magnetic adsorbent of the present invention: water content: 51wt% -55 wt%; wet apparent density: 0.73-0.78 g/ml; wet true density: 1.15-1.25 g/ml; particle size range: the grain diameter is 0.28-0.90 mm and the proportion is more than 95wt%; pH application range: 6 to 10.
The invention leads the surface water polluted by heavy metal to enter the magnetic adsorber through the pipeline filter for heavy metal adsorption, the adsorbent and the waste water enter the magnetic separator after heavy metal adsorption, and the purified effluent reaches the surface water environmental quality standard and is discharged. The separated magnetic adsorbent enters a magnetic adsorbent regenerator, and returns to the magnetic adsorbent regenerator for continuous use after physical regeneration. The removed sludge is sent to a unit with treatment qualification for disposal after filter pressing and dehydration.
The invention puts the iron-manganese-cerium-carried porous ceramic particles into a sodium hydroxide solution for oxidation reaction, so that ferrous iron and ferric iron are generated to generate ferroferric oxide and hydrated ferric oxide respectively.
According to the invention, a large number of oxygen vacancies are formed in the conversion process of 3-valent and 4-valent cerium to form a special iron-cerium-manganese hydrated oxide, iron is loaded to mainly remove arsenic, antimony and the like, manganese mainly removes lead, cadmium and the like, cerium is loaded with more hydrated oxides (such as hydrated iron oxide, hydrated manganese oxide and the like) by using valence-change characteristics, and thus a better heavy metal removal effect is achieved.
According to the invention, through the processes of magnetic adsorbent adsorption treatment, high-efficiency separation of the magnetic adsorbent and physical reinforcement regeneration of the adsorbent, the treated effluent meets the requirement of the environmental quality standard of the surface water, the regeneration and the repeated use of the magnetic adsorbent are realized, the problem of secondary pollution caused by the generation of a large amount of heavy metal-containing bottom mud and heavy metal-enriched plants is avoided, and the water quality safety of the surface water body is ensured.
Compared with the prior art, the invention has the beneficial effects that:
1) According to the invention, the heavy metal polluted surface water is subjected to the adsorption treatment by the magnetic adsorbent, the high-efficiency separation by the magnetic adsorbent and the physical reinforcement regeneration process of the adsorbent, the treated effluent meets the environmental quality standard requirement of the surface water, the regeneration and the repeated use of the magnetic adsorbent are realized, the problem of secondary pollution caused by the generation of a large amount of heavy metal-containing bottom mud and heavy metal-enriched plants is avoided, and the water quality safety of the surface water body is ensured.
2) In the preparation process of the magnetic adsorbent, ferrous ions form ferrous hydroxide under an alkaline condition, and ferroferric oxide with magnetism is formed under the condition of heating and slow oxidation.
3) The magnetic adsorbent is loaded with a special hydrated oxide of iron, cerium and manganese, and has different separation principles compared with an adsorbent loaded with simple substance iron.
4) The porous ceramic particles adopted by the invention are purchased from the market, are prepared from pure raw materials, and have obviously better adsorption property compared with a ceramic matrix prepared from waste materials.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1
A remediation method of heavy metal contaminated surface water, the remediation method comprising the steps of:
step 1, allowing heavy metal polluted surface water to pass through a pipeline filter and enter a magnetic adsorber for heavy metal adsorption, wherein the initial adding amount of the magnetic adsorbent is 400mg/L, and the adsorption time is 30min; the magnetic adsorbent is prepared by the following method:
1) Crushing and sieving purchased porous ceramic particles, and then putting a part with 30-100 meshes into a 0.3mol/L manganese sulfate solution with the volume 3 times that of the porous ceramic particles to soak for 1 hour to prepare manganese-loaded porous ceramic particles;
2) Putting the manganese-loaded porous ceramic particles into 0.1mol/L cerous nitrate solution with the volume 3 times that of the manganese-loaded porous ceramic particles, and soaking for 1 hour to prepare the manganese-loaded cerium porous ceramic particles;
3) Putting the manganese-cerium-loaded porous ceramic particles into 1mol/L potassium permanganate solution with the volume 3 times that of the manganese-cerium-loaded porous ceramic particles, soaking for 1 hour, and cleaning for 30 minutes to prepare manganese-cerium-oxide-loaded porous ceramic particles;
4) Putting the porous ceramic particles carrying manganese oxide and cerium into a mixed solution of 1.2mol/L ferrous sulfate and 1.2mol/L ferric sulfate which is 3 times of the volume of the porous ceramic particles carrying manganese oxide and cerium, and soaking for 2 hours to prepare the porous ceramic particles carrying iron, manganese and cerium;
5) Putting the Fe-Mn-Ce-loaded porous ceramic particles into 2mol/L sodium hydroxide solution with the volume 3 times that of the Fe-Mn-Ce-loaded porous ceramic particles for aeration oxidation reaction for 3 hours at the reaction temperature of 80 ℃ to prepare magnetic Fe-Ce-Mn-loaded porous ceramic particles;
6) And (3) washing the magnetic iron-cerium-manganese-loaded porous ceramic particles with clear water for 30 minutes, and air-drying at normal temperature for 3 days to prepare the magnetic heavy metal adsorbent.
And 2, the adsorbent and the wastewater enter a magnetic separator after heavy metal adsorption, an electric field is applied for 0.5T, the magnetic adsorbent is adsorbed on a magnetic plate, and the purified water reaching the environmental quality standard of surface water flows out from one side and enters a clean water tank for discharge.
And 3, after the magnetic field is separated, the magnetic adsorbent attracted on the magnetic plate enters a magnetic adsorbent regenerator. The regeneration time is 60min, wherein the operation process of the regenerator is as follows: the magnetic adsorbent entering the regenerator is in a fluidized state and is subjected to rotary flexible friction by the surrounding friction brush cloth. After physical regeneration, the adsorbent returns to the magnetic adsorber, and the removed sludge enters the excess sludge tank and is sent to a unit with treatment quality for disposal after filter pressing and dehydration.
The treatment effects (the unit of lead, cadmium, arsenic and antimony are all mg/L) are shown in Table 1,
TABLE 1
Example 2
A remediation method of heavy metal contaminated surface water, the remediation method comprising the steps of:
step 1, allowing heavy metal polluted surface water to enter a magnetic adsorber through a pipeline filter for heavy metal adsorption, wherein the initial adding amount of a magnetic adsorbent is 200mg/L, and the adsorption time is 60min; the magnetic adsorbent is prepared by the following method:
1) Crushing and sieving purchased porous ceramic particles, and then putting a part with 30-100 meshes into a manganese sulfate solution with the volume 5 times that of the porous ceramic particles and the concentration of 0.6mol/L for soaking for 2 hours to prepare manganese-loaded porous ceramic particles;
2) Putting the manganese-loaded porous ceramic particles into 0.2mol/L cerous nitrate solution with the volume 5 times that of the manganese-loaded porous ceramic particles, and soaking for 2 hours to prepare the manganese-loaded cerium porous ceramic particles;
3) Putting the manganese-cerium-loaded porous ceramic particles into 0.5mol/L potassium permanganate solution which is 5 times of the volume of the manganese-cerium-loaded porous ceramic particles, soaking for 2 hours, and cleaning for 10 minutes to prepare manganese-cerium-oxide-loaded porous ceramic particles;
4) Putting the porous ceramic particles carrying manganese oxide and cerium into a mixed solution of 0.8mol/L ferrous sulfate and 0.8mol/L ferric sulfate which is 5 times of the volume of the porous ceramic particles carrying manganese oxide and cerium, and soaking for 1 hour to prepare the porous ceramic particles carrying iron, manganese and cerium;
5) Putting the Fe-Mn-Ce-loaded porous ceramic particles into 1mol/L sodium hydroxide solution which is 5 times of the volume of the Fe-Mn-Ce-loaded porous ceramic particles, and carrying out aeration oxidation reaction for 2 hours at the reaction temperature of 40 ℃ to prepare magnetic Fe-Ce-Mn-loaded porous ceramic particles;
6) And (3) washing the magnetic iron-cerium-manganese-loaded porous ceramic particles with clear water for 10 minutes, and air-drying at normal temperature for 1 day to prepare the magnetic heavy metal adsorbent.
And 2, the adsorbent and the wastewater enter a magnetic separator after heavy metal adsorption, an electric field is applied for 0.1T, the magnetic adsorbent is adsorbed on a magnetic plate, and the purified water reaching the environmental quality standard of surface water flows out from one side and enters a clean water tank for discharge.
And 3, after the magnetic field is separated, the magnetic adsorbent attracted on the magnetic plate enters a magnetic adsorbent regenerator. The regeneration time is 60min, wherein the operation process of the regenerator is as follows: the magnetic adsorbent entering the regenerator is in a fluidized state and is subjected to rotary flexible friction by the surrounding friction brush cloth. After physical regeneration, the adsorbent returns to the magnetic adsorber, and the removed sludge enters the excess sludge tank and is sent to a unit with treatment quality for disposal after filter pressing and dehydration.
The treatment effects (in mg/L for each of lead, cadmium, arsenic and antimony) are shown in Table 2.
TABLE 2
Example 3
A remediation method of heavy metal contaminated surface water, the remediation method comprising the steps of:
step 1, allowing heavy metal polluted surface water to enter a magnetic adsorber through a pipeline filter for heavy metal adsorption, wherein the initial adding amount of a magnetic adsorbent is 300mg/L, and the adsorption time is 50min; the magnetic adsorbent is prepared by the following method:
1) Crushing and sieving purchased porous ceramic particles, and then putting a part with 30-100 meshes into a 0.5mol/L manganese sulfate solution with the volume 4 times that of the porous ceramic particles to soak for 1.5 hours to prepare manganese-loaded porous ceramic particles;
2) Putting the manganese-loaded porous ceramic particles into 0.15mol/L cerous nitrate solution with the volume 4 times that of the manganese-loaded porous ceramic particles, and soaking for 1.5 hours to prepare the manganese-loaded cerium porous ceramic particles;
3) Putting the manganese-cerium-loaded porous ceramic particles into 0.8mol/L potassium permanganate solution with the volume 4 times that of the manganese-cerium-loaded porous ceramic particles, soaking for 1.5 hours, and cleaning for 20 minutes to prepare manganese-cerium-loaded porous ceramic particles;
4) Putting the porous ceramic particles carrying the manganese oxide and the cerium oxide into a mixed solution of 1mol/L ferrous sulfate and 1mol/L ferric sulfate, which is 4 times of the volume of the porous ceramic particles carrying the manganese oxide and the cerium oxide, and soaking for 1.5 hours to prepare the porous ceramic particles carrying the iron, manganese and cerium;
5) Putting the Fe-Mn-Ce-loaded porous ceramic particles into a 1.5mol/L sodium hydroxide solution 4 times the volume of the Fe-Mn-Ce-loaded porous ceramic particles for aeration oxidation reaction for 2.5 hours at the reaction temperature of 60 ℃ to prepare magnetic Fe-Ce-Mn-loaded porous ceramic particles;
6) And (3) washing the magnetic iron-cerium-manganese-loaded porous ceramic particles with clear water for 20 minutes, and air-drying at normal temperature for 2 days to prepare the magnetic heavy metal adsorbent.
And 2, the adsorbent and the wastewater enter a magnetic separator after heavy metal adsorption, an electric field is applied for 0.3T, the magnetic adsorbent is adsorbed on a magnetic plate, and the purified water reaching the environmental quality standard of surface water flows out from one side and enters a clean water tank for discharge.
And 3, after the magnetic field is separated, the magnetic adsorbent attracted on the magnetic plate enters a magnetic adsorbent regenerator. The regeneration time is 60min, wherein the operation process of the regenerator is as follows: the magnetic adsorbent entering the regenerator is in a fluidized state and is subjected to rotary flexible friction by the surrounding friction brush cloth. After physical regeneration, the adsorbent returns to the magnetic adsorber, and the removed sludge enters a residual sludge tank and is sent to a unit with treatment quality for disposal after filter pressing and dehydration.
The treatment effects (in mg/L for each of lead, cadmium, arsenic and antimony) are shown in Table 3.
TABLE 3
The method can be realized by upper and lower limit values and interval values of intervals of process parameters (such as temperature, time and the like), and embodiments are not listed.
Conventional technical knowledge in the art can be used for the details which are not described in the present invention.
Any feature disclosed in this specification may be replaced by alternative features serving an equivalent or similar purpose, unless expressly stated otherwise. Unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features. The description is only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that the technical solutions of the present invention may be modified or substituted with equivalents without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered by the scope of the claims of the present invention.
Claims (6)
1. A remediation method of heavy metal contaminated surface water, the remediation method comprising the steps of:
adsorbing heavy metal polluted surface water by using a magnetic adsorbent, carrying out magnetic separation on the magnetic adsorbent adsorbing the heavy metal and the purified surface water, adsorbing the magnetic adsorbent on a magnetic plate, and feeding the purified surface water into a clean water tank; the magnetic adsorbent on the magnetic plate is regenerated and then reused;
the preparation method of the magnetic adsorbent comprises the following steps:
1) Putting 30-100 mesh porous ceramic particles into 0.3-0.6 mol/L manganese salt aqueous solution which is 3~5 times of the volume of the porous ceramic particles, and soaking for 1~2 hours to prepare manganese-loaded porous ceramic particles;
2) Putting the manganese-loaded porous ceramic particles into 0.1 to 0.2mol/L cerous nitrate solution which is 3~5 times the volume of the manganese-loaded porous ceramic particles, and soaking for 1~2 hours to prepare the manganese-loaded porous ceramic particles;
3) Putting the porous ceramic particles carrying manganese and cerium into 0.5 to 1mol/L potassium permanganate solution which is 3~5 times the volume of the porous ceramic particles carrying manganese and cerium, soaking for 1~2 hours, and cleaning for 10 to 30 minutes to prepare the porous ceramic particles carrying manganese oxide and cerium;
4) Putting the porous ceramic particles carrying manganese oxide cerium into 0.8 to 1.2mol/L ferric salt aqueous solution with the volume of 3~5 times of the porous ceramic particles carrying manganese oxide cerium, and soaking for 1~2 hours to prepare the porous ceramic particles carrying iron, manganese and cerium;
5) Putting the iron-manganese-cerium-loaded porous ceramic particles into 1-2mol/L sodium hydroxide solution which is 3~5 times of the volume of the iron-manganese-cerium-loaded porous ceramic particles, and carrying out aeration oxidation reaction for 2~3 hours at the reaction temperature of 40-80 ℃ to prepare magnetic iron-manganese-loaded porous ceramic particles;
6) Washing the magnetic iron-carrying cerium-manganese porous ceramic particles with clear water for 10 to 30 minutes, and air-drying the particles at normal temperature for 1~3 days to obtain a magnetic adsorbent;
the magnetic adsorbent comprises: water content: 51wt% -55 wt%; wet apparent density: 0.73 to 0.78g/mL; wet and true density: 1.15 to 1.25g/mL; particle size range: the grain diameter is 0.28 to 0.90mm, and the proportion is more than 95wt%; pH application range: 6 to 10;
putting the iron-manganese-cerium-loaded porous ceramic particles into a sodium hydroxide solution for oxidation reaction, so that ferrous iron and ferric iron generate ferroferric oxide and hydrated ferric oxide respectively;
the iron salt is ferrous salt and ferric salt.
2. The repairing method according to claim 1, wherein the amount of the magnetic adsorbent is 200mg/L to 400mg/L and the adsorption time is 30min to 60min during the magnetic adsorbent adsorption treatment.
3. The repair method according to claim 1, wherein the applied magnetic field at the time of magnetic separation is 0.1 to 0.5T.
4. The repair method according to claim 1, wherein the regeneration is in particular: and (3) the magnetic adsorbent is in a fluidized state, sludge on the magnetic adsorbent is removed, and the regeneration time is 30min to 60min.
5. Repair method according to claim 1, characterized in that the manganese salt is manganese sulfate and/or manganese chloride.
6. The repair method according to claim 1, wherein the divalent iron salt is ferrous sulfate and/or ferrous chloride; the ferric salt is ferric sulfate and/or ferric chloride.
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